CN1842934A - Solid oxide fuel cell device with a component having a protective coatings and a method for making such - Google Patents
Solid oxide fuel cell device with a component having a protective coatings and a method for making such Download PDFInfo
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- CN1842934A CN1842934A CNA2004800245624A CN200480024562A CN1842934A CN 1842934 A CN1842934 A CN 1842934A CN A2004800245624 A CNA2004800245624 A CN A2004800245624A CN 200480024562 A CN200480024562 A CN 200480024562A CN 1842934 A CN1842934 A CN 1842934A
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- fuel cell
- metal
- cell device
- solid oxide
- oxide fuel
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- 239000000446 fuel Substances 0.000 title claims abstract description 50
- 239000007787 solid Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 26
- 239000011253 protective coating Substances 0.000 title abstract 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims description 56
- 239000011651 chromium Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 47
- 230000003647 oxidation Effects 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 239000011247 coating layer Substances 0.000 claims description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 22
- 238000002048 anodisation reaction Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000007743 anodising Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- -1 oxonium ions Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 206010011376 Crepitations Diseases 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001996 bearing alloy Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910003026 (La,Sr)(Co,Fe)O3 Inorganic materials 0.000 description 1
- 229910002439 Ce0.8Sm0.2O1.9 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- LEQZGTOEYZBNNG-UHFFFAOYSA-K chromium(3+);trihydroxide;trihydrate Chemical compound O.O.O.[OH-].[OH-].[OH-].[Cr+3] LEQZGTOEYZBNNG-UHFFFAOYSA-K 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
A solid oxide fuel cell device comprises: (a) zirconia based electrolyte; (b) at least one ectrode situated on the electrolyte; (c) a component situated in close proximity to the electrolyte, the component comprising at least one metal or metal oxide capable, at temperatures of above 625 DEG C, of: (i) migrating to the surface of this component, and (ii) being re-deposited on said at least one electrode; and (d) a protective coating situated on at least one surface of this component. The protective coating substantially prevents the at least one metal or metal oxide from leaving the surface of the component, which is situated under said protective coating. The protective coating is also being substantially impermeable to oxygen.
Description
Invention field
The present invention relates in the coating that is applicable on the metal parts of fuel-cell device the protective finish on the electrolytical stainless steel frame that is used for being supported in the Solid Oxide Fuel Cell.
Technical field
In recent years, use Solid Oxide Fuel Cell is the problem of big quantity research always.The conventional components of Solid Oxide Fuel Cell (SOFC) comprises the electrolyte that is clipped in two charged oxonium ions of conduction between the electrode.In this battery,, make hydrogen and the oxonium ion reaction of conducting produce electric current by electrolyte by in for example oxidation of hydrogen of anode (anode) fuel.Oxygen molecule is by producing oxonium ion in negative electrode (cathode) reduction.
Known base type (substrate) Solid Oxide Fuel Cell uses metal alloy as dividing plate sometimes.For example at Yoshido Matsuzaki and Isami Yasuda, the title of Solid State Ionics 132 (2000) 271-278 has been described this structure in the paper of " Electromagnetic properties of a SOFC cathode in contact with a chromium-containingalloy separator (electromagnetic property when the SOFC negative electrode contacts with the chrome-bearing alloy dividing plate) ".This paper has been described when the alloy that forms chromium is used as dividing plate, and the performance of SOFC negative electrode descends rapidly owing to " Cr poisoning ".
Yoshido Matsuzaki and Isami Yasuda are at Journal ofElectrochemical Society, 148 (2) A126-A131 (2001), title is for also having described the problem of " Cr poisoning " in " Dependence of SOFC cathode Degradation byChromium-Containing Alloy on Compositions of Electrodes and Electrolyte (dependence that electrolyte is formed electrode and electrolyte because of the variation of chrome-bearing alloy SOFC negative electrode) ".More specifically, this paper is pointed out " should pay close attention to the oxide fouling (Cr that forms from most of high-temperature alloys surface
2O
3) oxygen chromium hydroxide (chromium oxyhydroxide) steam that contains that go up to produce is reduced in the cathode performance under the polarization condition ".This article is also pointed out, finds that the amount of decreased performance depends on polarization, prepares the composition of electrolyte of electrodes thereon.This paper proposes, and poisons in order to reduce Cr, uses La respectively
0.6Sr
0.4Fe
0.8O
3And Ce
0.8Sm
0.2O
1.9As electrode and electrolyte.
S.P.Jiang etc. also describe the problem of Cr deposition on the electrode in the paper of title for " comparative studies of deposition chromium on the air electrode in Solid Oxide Fuel Cell " of Journal ofEuropean Ceramic Society (2002) 361-373.More specifically, this paper points out that " studied and forming in the presence of the alloy interconnect of chromium in 900 ℃ of air flow, the deposition process of chromium (Cr) material is at (La, Sr) MnO
3(LSM), Pt and (La, Sr) (Co, Fe) O
3(LSCF) O on the electrode
2Reduction.To the reaction on the LSM electrode, Cr material preferential deposition form tangible deposition ring at the edge of LSM electrode, and on the LSCF electrode, the Cr electrodeposition substance forms independent Cr particle at electrode and bath surface on the Zirconia electrolytic surface.On the contrary, to the O on the Pt electrode
2Reduction, all not having at electrode and bath surface can detected Cr electrodeposition substance ".That is, this paper propose for eliminate or minimizing and Cr in the relevant problem of the deposition of electrolyte/electrode surface, limit by certain material manufacturing electrode/electrolyte.
Known, under sufficiently high temperature (725 ℃ and higher according to appointment), by the zirconia YSZ (Y of stabilized with yttrium oxide
2O
3-ZrO
2) good ionic conductance and the extremely low electronic conductance of electrolyte demonstration.United States Patent (USP) 5,273,837 describe the Solid Oxide Fuel Cell that forms heat shock resistance with this composition.
U.S. Patent bulletin US2002/0102450 describes and comprises the solid electrolyte fuel cell that improved electrode-electric is separated the matter structure.This structure comprises the solid electrolyte sheet that combines a plurality of positive electrodes and negative electrode, and this positive electrode and negative electrode are fixed on the opposite face of thin flexible inorganic electrolyte sheet.An example explanation electrode does not form pantostrat on electrolyte sheet, but limits a plurality of distinct area or band.These zones are electrical communication by the electric conductor of contact with it, and described electric conductor runs through the through hole in the electrolyte sheet.Through hole is filled with electric conducting material (via interconnects).
Summary of the invention
One aspect of the invention provides a kind of solid oxide fuel cell device, and this device comprises:
(a) zirconium oxide base electrolyte;
(b) at least one electrode on this electrolyte;
(c) near these electrolytical parts, these parts comprise at least a metal or metal oxide, described metal or metal oxide be higher than 625 ℃ temperature can:
(i) move to these parts the surface and
(ii) be deposited on again on described at least one electrode;
(d) at least one lip-deep protective finish of this parts.This protective finish can prevent substantially that at least a metal or metal oxide from leaving the surface of these parts, described metal or metal oxide be positioned at described protective finish below.Protective finish is oxygen flow not basically.
Another aspect the present invention includes a kind of method of making solid oxide fuel cell device, and this method may further comprise the steps:
(e) provide zirconium oxide base electrolyte, on this electrolyte, have at least one negative electrode;
(f) be provided at the parts that protective finish is arranged on its at least one surface, described parts are near described electrolyte, this radius comprises at least a metal, this at least a metal is in the temperature that is higher than 625 ℃, when not having described protective finish can: (i) move to the described surface of described parts and (ii) depositing to again on described at least one negative electrode with the oxide of described metal or described metal; Wherein, described protective finish has prevented that basically described at least a metal from leaving described surface, and described coating is oxygen flow not basically also.
According to an embodiment of the invention, be provided at the step that its at least one surface has the parts of protective finish and comprise: (i) in the coating of described parts surface coating 1-100 μ m, this coating becomes oxygen impermeable after the oxidation; (ii) this coating of oxidation obtains described protective finish.
The present invention adopt an advantage of the solid oxide fuel cell device of protective finish be owing to make from the containing metal parts surface discharge do not need metal for example Cr be minimum improved performance is provided.This containing metal parts can be the metal alloy dividing plates that for example is used for supporting electrolytical stainless steel frame, cross tie part or uses in fuel-cell device.According to an embodiment of the invention, protective finish is that thickness is the aluminum oxide coating layer of 1-100 μ m.
Describe other features and advantages of the present invention below in detail, by these explanations, these feature and advantage to those skilled in the art, part is conspicuous, perhaps, comprise that following detailed description, claims and accompanying drawing enforcement the present invention recognize these feature and advantage by by described herein.
The general introduction and the following detailed that should be understood that the front provide example embodiment of the present invention, aim to provide summary or the framework of understanding desired character of the present invention and characteristic.Accompanying drawing provides further understanding of the invention, accompanying drawing can in conjunction with and constitute the part of this specification.Description of drawings the embodiments of the present invention, and be used for illustrating principle of the present invention and operation with specification.
The accompanying drawing summary
The schematic cross-section of Fig. 1 one embodiment of the present invention;
Fig. 2 A-2D is the surface picture that aluminum oxide coating layer (on 446 stainless steels) that electrochemistry produces amplifies 50 times, 200 times, 500 times and 2000 times respectively.
The aluminum oxide coating layer of Fig. 3 A-3D thermal oxidation (on 446 stainless steels) amplifies the surface picture of 50 times, 200 times, 500 times and 2000 times respectively.
The detailed description of preferred implementation
With reference to preferred implementation of the present invention, example wherein is shown in accompanying drawing in detail.As possible, in institute's drawings attached, adopt identical reference numerals to represent identical or similar parts.
An execution mode of solid oxide fuel cell device of the present invention is shown in Fig. 1, and with reference numerals 10 expressions.Solid oxide fuel cell device 10 comprises: (a) zirconium oxide base electrolyte 20; (b) at least one is positioned at the electrode 30 on this electrolyte; (c) near the parts 50 of electrolyte 20.These parts 50 comprise at least a metal or metal oxide, this metal or metal oxide be higher than under 625 ℃ the temperature can: (i) move to the surface 52 of these parts, (ii) deposit to again on electrode and/or other parts.Protective finish 60 is positioned on the surface 52 of these parts 50.Protective finish 60 prevents that basically a kind of metal or metal oxide from leaving the surface 52 under the described protective finish 60 of being positioned at of parts 50.Protective finish 60 is oxygen flow not basically also.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1
Solid oxide fuel cell device 10 shown in Figure 1 comprises: (a) yittrium oxide-stable zirconia (YSZ) electrolyte sheet 20; (b) a plurality of electrodes 30 that are positioned on the electrolyte sheet 20, described electrode comprises at least one negative electrode 32; (c) the support fixation electrolyte sheet 20 thereon and the metal framework 50 of electrode 30.In this execution mode, electrolyte sheet 20 supports 34 pairs on a plurality of negative electrode 32-anodes, and has a plurality of through holes of filling via interconnects 36.
Embodiment 2
Can adopt several different methods to prepare aluminium oxide protective finish 60.For example, can adopt the electrochemical oxidation of aluminum metal.At first electro-deposition of aluminum metal (using nickel strike plating (nickel strike)) is at parts 50, for example on the stainless steel frame of embodiment 1.Aluminium coat can be formed with the organic molten salt mixture with by the solution electroplating of aluminium at some organic solvent by inorganic.Commercially available electroplated aluminum equipment for example can be from AlumiPlate, Inc.of 8960 Springbrook Dr., and Minneapolis, the MN 55433-5874 U.S. buys.
In this embodiment, employing Ni strike plating obtains the good aluminium coat on 446 stainless steels.Subsequently, be aluminium oxide with aluminium (Al) coating electrochemical oxidation (anodization).Perhaps, by electroplate and subsequently thermal oxidation Al coating can form aluminum oxide coating layer.But anodization is relevant with aluminium usually, and similarly method can be used for other base metal, comprises magnesium, titanium and zinc.These metals also can form protective finish 60.
Can in various electrolyte solutions, adopt different operating conditions to comprise the concentration and the composition of electrolyte solution, have any additives, temperature, voltage and current intensity is carried out anodization to aluminium.Following three kinds of main anodization process are arranged: (a) use chromic acid as electrolytical chromium method, (b) sulfuric acid process of at room temperature carrying out, and (c) only use sulfuric acid or additive is arranged, hard anodizing (hard anodizing) method of under low temperature (0 ℃ or lower), carrying out usually.
To this execution mode of the present invention, we have adopted the method for hard anodizing.The main difference of sulfuric acid process and hard anodizing method is operating temperature, uses additive, and the voltage and current density when carrying out anodization.The hard anodizing method is also referred to as hard conating or the anodization of III type, produces thick relatively coating, conventional then sulfur acid anodizing.In our test, can form maximum aluminum oxide coating layers to 100 μ m thickness.In this execution mode,, use 20-35mA/cm 0-10 ℃ of temperature
2Current density is carried out anodization.The voltage that produces in the constant current mode can reach the highest 100 volts when finishing near this process.If initial aluminum metal layer is high-quality, this method produces the high quality aluminum oxide layer of high density (low voidage or voidage are 0).Fig. 2 A-2D is the surface picture that the thick aluminum oxide coating layer (on 446 stainless steels) of 100 μ m that electrochemistry produces amplifies 50 times, 200 times, 500 times and 2000 times respectively.Because this coating is thicker, can see the very thin crackle of existence in coating.Cr, Ni and Fe are represented to exist in clear zone in the photo.Fig. 2 C illustrates along little (identical) part of one of these crackles with 2D and forms chromium.The possibility that thin protective finish 60 cracks is less, therefore preferred thin coating.
Fig. 2 A shows and bright contains the chromium district seldom.Therefore, even illustrate and have these crackles, most coating surface does not contain chromium.Therefore, the aluminum oxide coating layer that produces by the electrochemical oxidation aluminium lamination has solved the problem of oxidation of the stainless steel component in solid oxide fuel cell stack.Although exist aluminum oxide coating layer that battery performance is had negative effect, prevented that chromium from losing and being deposited on other battery component subsequently again.
The another kind of method that produces aluminum oxide coating layer is the thermal oxidation by the aluminium lamination of oxidation on substrate (for example, 446 stainless steels).This method is exposed to aluminium lamination reasonable time (1-5 hour) in the oxygen of high temperature (800 ℃).Fig. 3 A-3D is the surface picture that the aluminum oxide coating layer (on 446 stainless steels) of the 10-20 μ m thickness that produces of thermal oxidation amplifies 50 times, 200 times, 500 times and 2000 times respectively.This also is good coating, has only seldom expression to have the clear zone of Cr, Ni and Fe.(referring to Fig. 3 A), in the method, because high temperature, some aluminium are diffused in the steel, may prevent that crackle from forming and forming good adhesion.(anodization of part electrochemistry, thermal oxidation subsequently) combination of two kinds of methods can be avoided crackle, forms better to adhere to, and simultaneously, does not in fact make the Cr porous by protective finish 60.
More specifically, compare these two kinds of methods with identical initial aluminum coating (100 μ m are thick).Two kinds of methods all obtain good result.Measure the effect of estimating protective finish 60 at the Cr that alumina surface exists by being exposed to high temperature (800 ℃) after 1-5 hour.Protective finish 60 prevents to form chromium on framework 50 surfaces.Therefore, because this protective finish 60, seldom or do not have a chromium (Cr
2O
3) be deposited on the electrode.Preferred at least 70% coating surface is long-pending, therefore is that at least 70% negative electrode and/or bath surface of oxid fuel cell device do not covered by chromium.Be more preferably, 85% coating surface is long-pending, is that at least 85% bath surface is not covered by chromium therefore.Preferably at least 90% coating surface is long-pending with therefore at least 90% negative electrode and/or bath surface are not covered by chromium.Most preferably at least 98% coating surface long-pending and therefore 98% cathode surface do not covered by chromium.
The applicant finds that also for meeting the requirements of protection, non-conductive aluminum oxide coating layer has required minimum thickness.The applicant has tested the aluminum oxide coating layer of 0.5 μ m.Thin aluminum oxide coating layer is not enough to prevent form chromium oxide on the steel surface.Too thick aluminum oxide coating layer may be cracked because the thermal coefficient of expansion (CTE) of aluminium and stainless thermal coefficient of expansion have very big-difference when thermal cycle.Yet thin aluminum oxide coating layer is pliable and tough, is not easy cracked when thermal cycle.Therefore, need select best thickness to the coating of protecting, simultaneously, can not be too thick so that cracked when thermal cycle.Therefore, the thickness of protective finish 60 is preferably 1-100 μ m.Preferred coating layer thickness is less than 30 μ m.More preferably coating layer thickness is 1-20 μ m, most preferably is 5-20 μ m.Optimum thickness is about 10 μ m.
Iron-chrome-aluminium-alloy (as stainless steel 406) also can produce aluminum oxide coating layer when oxidation, therefore form protective finish, prevents that chromium from occurring on the surface.Therefore but the thermal coefficient of expansion of iron-chrome-aluminium-alloy is as shown in the table greater than Zirconia electrolytic, is not suitable for use in the parts in some fuel cell structure, used framework in the Solid Oxide Fuel Cell as shown in Figure 1.
Table 1 provides the CTE to some material in these materials.
Table 1
| Material | CTE |
| ZrO 2Electrolyte | 11.4×10 -6/℃ |
| The Fe-20%Cr446 stainless steel | 11.6×10 -6/℃ |
| The Fe-20%Cr-5%Al alloy | 14.5×10 -6/℃ |
Also can use other protective finish, as glass or zirconia base coating.These coatings are oxygen flow ion not substantially also, and prevents the Cr oxidation and form chromium oxide Cr
2O
3An example of this coating is that the metal oxide that forms according to following mode is (as ZrO
2, Al
2O
3, YSZ) basic coating: (i) by clean, smear or dipping with sponge, apply be suspended in solvent for example the metal oxide in the pentyl acetate (as ZrO
2, Al
2O
3, YSZ) powder; The (ii) optional uniformity of using scraper to guarantee coating; (iii) sintering forms hard protective finish 60.The another kind of method of using this coating is plasma spray coating-optional sintering step subsequently.
According to the present invention, the method for manufacturing solid oxide fuel cell device of the present invention may further comprise the steps:
(g) provide the zirconium oxide base electrolyte 20 that has at least one negative electrode 32 on it;
(h) be provided at the parts 50 that protective finish 60 is arranged on its at least one surface 52, described coating 60 is oxygen flow ion not substantially;
(i) position of parts 50 is near electrolyte 60.Parts 50 comprise at least a metal 70, this metal when not having described protective finish, in the temperature that is higher than 625 ℃, can:
(i) move to the described surface of these parts 50,
(ii) deposit to again on the negative electrode 32 with described metal or its oxide; Wherein said protective finish prevents that basically this metal or this metal oxide from leaving surface 52.
According to an execution mode, be provided at the step that its at least one surface 52 has the parts of protective finish 60 and also comprise: (i) have the coating surface 52 of 1-100 μ m coating, behind this coating oxidation, become oxygen impermeable; (ii) this coating is carried out oxidation, obtain described protective finish 60.
According to an embodiment, oxidation step is electrochemical oxidation (anodization).According to another embodiment, oxidation step is thermal oxidation.According to an embodiment, coating step is included in surface deposition aluminium, and step of thermal oxidation produces fine and close aluminum oxide coating layer.
All be apparent not departing from the various modifications and changes of under the spirit and scope of the invention the present invention being carried out to those skilled in the art.Therefore, the present invention is intended to be included within the scope of appended claims and its content of equal value to modification of the present invention and change.
Claims (23)
1. solid oxide fuel cell device, it comprises:
(a) zirconium oxide base electrolyte;
(b) at least one electrode on described electrolyte;
(c) near described electrolytical parts, described parts comprise at least a metal or metal oxide, described metal or metal oxide be higher than under 625 ℃ the temperature can,
(i) move to the surface of described parts, and
(ii) be deposited on again on described at least one electrode;
(d) at least one lip-deep protective finish of described parts, described coating has prevented that substantially described at least a metal or metal oxide from leaving the surface under described protective finish in the described parts, and described protective finish is oxygen flow not substantially also.
2. solid oxide fuel cell device as claimed in claim 1 is characterized in that, the thickness of described protective finish is less than 100 μ m.
3. solid oxide fuel cell device as claimed in claim 1 is characterized in that, the thickness of described protective finish is 1-30 μ m.
4. solid oxide fuel cell device as claimed in claim 1 is characterized in that, the thickness of described protective finish is 5-20 μ m.
5. solid oxide fuel cell device as claimed in claim 1 is characterized in that, described at least a metal is Cr, and described protective finish is selected from Al
2O
3, glass, zirconia and stabilized with yttrium oxide the oxide of zirconia, magnesium, titanium and zinc.
6. solid oxide fuel cell device as claimed in claim 5 is characterized in that, the thickness of described coating is 1-100 μ m.
7. solid oxide fuel cell device as claimed in claim 1 is characterized in that, at least 90% electrode surface is not covered by the oxide of described at least a metal.
8. solid oxide fuel cell device as claimed in claim 1 is characterized in that described protective finish is a non-conductive coating layer.
9. solid oxide fuel cell device, it comprises:
(a) zirconium oxide base electrolyte;
(b) at least one negative electrode on described electrolyte;
(c) support described electrolytical metal framework, described metal framework comprises at least a metal, described metal be higher than under 625 ℃ the temperature can:
(i) move to described framework surface,
(ii) oxidation, and
(iii) be deposited on again on described at least one negative electrode with oxide form;
(d) protective finish on described stainless steel frame, described coating have prevented that substantially described metal from leaving described metal framework, also not saturating substantially described metal of described coating or oxygen.
10. solid oxide fuel cell device as claimed in claim 9 is characterized in that, the thickness of described coating is 1-100 μ m.
11. solid oxide fuel cell device as claimed in claim 9 is characterized in that, metal framework is the stainless steel metal framework, and described at least a metal is Cr, and described protective finish is selected from: Al
2O
3, glass, zirconia and stabilized with yttrium oxide zirconia.
12. solid oxide fuel cell device as claimed in claim 11 is characterized in that, described coating is a non-conductive coating layer, and its thickness is 1-100 μ m.
13. solid oxide fuel cell device as claimed in claim 11 is characterized in that, at least 70% coating surface is not covered by chromium.
14. solid oxide fuel cell device as claimed in claim 11 is characterized in that, at least 85% coating surface is not covered by chromium.
15. solid oxide fuel cell device as claimed in claim 11 is characterized in that, at least 90% coating surface is not covered by chromium.
16. solid oxide fuel cell device as claimed in claim 9 is characterized in that, the thermal coefficient of expansion CTE of described metal framework is 10 * 10
-6/ ℃ to 12.5 * 10
-6/ ℃.
17. solid oxide fuel cell device as claimed in claim 16 is characterized in that, the CTE of described metal framework is 11 * 10
-6/ ℃ to 12 * 10
-6/ ℃.
18. solid oxide fuel cell device as claimed in claim 17 is characterized in that, the thermal coefficient of expansion CTE of described metal framework is 11.2 * 10
-6/ ℃ to 11.7 * 10
-6/ ℃.
19. solid oxide fuel cell device as claimed in claim 9 is characterized in that, described protective finish is a non-conductive coating layer, and described metal framework is not an electric connector.
20. a method of making solid oxide fuel cell device, it may further comprise the steps:
(a) provide zirconium oxide base electrolyte, at least one negative electrode is arranged on this electrolyte;
(b) be provided at the parts that have protective finish on its at least one surface, described parts are near described electrolyte, and described parts comprise at least a metal, and this at least a metal is being higher than under 625 ℃ the temperature, do not have under the described protective finish situation can,
(i) move to the described surface of described parts,
(ii) oxidation, and
(iii) be deposited on again on described at least one negative electrode with described metal or described metal oxide form; Wherein protective finish has prevented that basically described at least a metal or this metal oxide from leaving described surface, and described coating is oxygen flow not basically also.
21. the method for manufacturing solid oxide fuel cell device as claimed in claim 20, it is characterized in that, the described step that has the parts of protective finish on its at least one surface that is provided at also comprises: (i) apply the coating of 1-100 μ m at described parts surface, become not oxygen flow behind this coating oxidation; (ii) this coating is carried out oxidation, to obtain described protective finish.
22. the method for manufacturing solid oxide fuel cell device as claimed in claim 21 is characterized in that, described coating step is included in described surface deposition aluminium, and described oxidation step produces fine and close aluminum oxide coating layer.
23. the method for manufacturing solid oxide fuel cell device as claimed in claim 21 is characterized in that, described oxidation step is selected from electrochemical oxidation and thermal oxidation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/648,415 US7314678B2 (en) | 2003-08-25 | 2003-08-25 | Solid oxide fuel cell device with a component having a protective coatings and a method for making such |
| US10/648,415 | 2003-08-25 | ||
| PCT/US2004/024401 WO2005024986A2 (en) | 2003-08-25 | 2004-07-28 | Solid oxide fuel cell device wth a component having a protective coating and method for making such |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1842934A true CN1842934A (en) | 2006-10-04 |
| CN1842934B CN1842934B (en) | 2011-09-21 |
Family
ID=34216724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800245624A Expired - Fee Related CN1842934B (en) | 2003-08-25 | 2004-07-28 | Solid oxide fuel cell device with a component having a protective coatings and a method for making such |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7314678B2 (en) |
| EP (1) | EP1671392A2 (en) |
| CN (1) | CN1842934B (en) |
| CA (1) | CA2535758A1 (en) |
| TW (1) | TWI253779B (en) |
| WO (1) | WO2005024986A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257665A (en) * | 2008-12-19 | 2011-11-23 | 巴特尔纪念研究院 | Cassette less sofc stack and method of assembly |
| CN105593413A (en) * | 2013-08-13 | 2016-05-18 | 索夫科能量股份公司 | Method for depositing layer of material onto metallic support for fuel cells or electrolysis cells |
| CN112028627A (en) * | 2020-08-13 | 2020-12-04 | 珠海粤科京华科技有限公司 | Firing method of solid electrolyte sheet and product |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10358458B4 (en) * | 2003-12-13 | 2010-03-18 | Elringklinger Ag | Fuel cell stack and method of manufacturing a fuel cell stack |
| DE102005030925A1 (en) * | 2005-07-02 | 2007-01-04 | Forschungszentrum Jülich GmbH | Chromium retention layers for components of fuel cell systems |
| KR100716369B1 (en) * | 2005-11-10 | 2007-05-11 | 현대자동차주식회사 | Method for manufacturing diesel catalyzed particulate filter |
| WO2007062117A2 (en) * | 2005-11-23 | 2007-05-31 | The Regents Of The University Of California | Electrochemical cell holder and stack |
| DE102006031863A1 (en) * | 2006-07-10 | 2008-01-17 | Webasto Ag | Fuel cell system and device for the media supply of a fuel cell assembly |
| US7781120B2 (en) * | 2007-05-16 | 2010-08-24 | Corning Incorporated | Thermo-mechanical robust solid oxide fuel cell device assembly |
| WO2009139833A2 (en) * | 2008-05-16 | 2009-11-19 | Corning Incorporated | Aluminide barrier layers and methods of making and using thereof |
| TWI384678B (en) * | 2008-10-14 | 2013-02-01 | Shu Feng Lee | Rapid set-up, double chamber detecting device of solid oxide fuel cell positive-electrolyte-negative (pen) plate |
| WO2012033491A1 (en) * | 2010-09-09 | 2012-03-15 | Utc Power Corporation | Fuel cell coating |
| TWI426644B (en) * | 2011-09-09 | 2014-02-11 | Metal Ind Res & Dev Ct | Metal deposition protection device for electrode plate and protection method thereof |
| US9559366B2 (en) * | 2014-03-20 | 2017-01-31 | Versa Power Systems Ltd. | Systems and methods for preventing chromium contamination of solid oxide fuel cells |
| US10084192B2 (en) | 2014-03-20 | 2018-09-25 | Versa Power Systems, Ltd | Cathode contact layer design for preventing chromium contamination of solid oxide fuel cells |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089455A (en) | 1989-08-11 | 1992-02-18 | Corning Incorporated | Thin flexible sintered structures |
| US5519191A (en) | 1992-10-30 | 1996-05-21 | Corning Incorporated | Fluid heater utilizing laminar heating element having conductive layer bonded to flexible ceramic foil substrate |
| US5273837A (en) | 1992-12-23 | 1993-12-28 | Corning Incorporated | Solid electrolyte fuel cells |
| DE4410711C1 (en) * | 1994-03-28 | 1995-09-07 | Forschungszentrum Juelich Gmbh | Metallic bipolar plate for HT fuel cells and method of manufacturing the same |
| DE19547699C2 (en) | 1995-12-20 | 2000-01-13 | Forschungszentrum Juelich Gmbh | Bipolar plate with selective coating |
| AUPO897897A0 (en) | 1997-09-05 | 1997-09-25 | Ceramic Fuel Cells Limited | An interconnect device for a fuel cell assembly |
| DE69905019T2 (en) | 1998-02-27 | 2003-10-16 | Corning Inc., Corning | FLEXIBLE INORGANIC ELECTROLYTIC FUEL CELL DESIGN |
| DE29807832U1 (en) | 1998-04-30 | 1998-07-02 | Siemens AG, 80333 München | High temperature fuel cell and high temperature fuel cell stack |
| AUPQ078899A0 (en) | 1999-06-04 | 1999-06-24 | Ceramic Fuel Cells Limited | A fuel cell gas separator |
| EP1113518B1 (en) | 1999-12-27 | 2013-07-10 | Corning Incorporated | Solid oxide electrolyte, fuel cell module and manufacturing method |
| US6852436B2 (en) | 2000-05-18 | 2005-02-08 | Corning Incorporated | High performance solid electrolyte fuel cells |
| US20020127460A1 (en) * | 2001-03-08 | 2002-09-12 | The Regents Of The University Of California | Protective coatings for fuel cell interconnect |
| WO2002088434A1 (en) | 2001-04-30 | 2002-11-07 | Alumiplate Incorporated | Aluminium electroplating formulations |
| US20030096147A1 (en) * | 2001-11-21 | 2003-05-22 | Badding Michael E. | Solid oxide fuel cell stack and packet designs |
-
2003
- 2003-08-25 US US10/648,415 patent/US7314678B2/en not_active Expired - Fee Related
-
2004
- 2004-07-28 WO PCT/US2004/024401 patent/WO2005024986A2/en active Application Filing
- 2004-07-28 CN CN2004800245624A patent/CN1842934B/en not_active Expired - Fee Related
- 2004-07-28 CA CA002535758A patent/CA2535758A1/en not_active Abandoned
- 2004-07-28 EP EP04786131A patent/EP1671392A2/en not_active Withdrawn
- 2004-08-20 TW TW093125393A patent/TWI253779B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257665A (en) * | 2008-12-19 | 2011-11-23 | 巴特尔纪念研究院 | Cassette less sofc stack and method of assembly |
| CN105593413A (en) * | 2013-08-13 | 2016-05-18 | 索夫科能量股份公司 | Method for depositing layer of material onto metallic support for fuel cells or electrolysis cells |
| CN112028627A (en) * | 2020-08-13 | 2020-12-04 | 珠海粤科京华科技有限公司 | Firing method of solid electrolyte sheet and product |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200524207A (en) | 2005-07-16 |
| TWI253779B (en) | 2006-04-21 |
| WO2005024986A2 (en) | 2005-03-17 |
| US20050048357A1 (en) | 2005-03-03 |
| US7314678B2 (en) | 2008-01-01 |
| EP1671392A2 (en) | 2006-06-21 |
| CN1842934B (en) | 2011-09-21 |
| WO2005024986A3 (en) | 2005-12-29 |
| CA2535758A1 (en) | 2005-03-17 |
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